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Potential-Dependent Competitive Electroreduction of CO(2) into CO and Formate on Cu(111) from an Improved H Coverage-Dependent Electrochemical Model with Explicit Solvent Effect

[Image: see text] An improved density functional theory-based H coverage-dependent electrochemical model with explicit solvent effect is proposed for Cu(111), which is used to identify potential-dependent initial competitive CO(2) electroreduction pathways considering HER. We find that a chemisorbed...

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Autores principales: Ou, Lihui, He, Zixi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7288361/
https://www.ncbi.nlm.nih.gov/pubmed/32548457
http://dx.doi.org/10.1021/acsomega.0c00227
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author Ou, Lihui
He, Zixi
author_facet Ou, Lihui
He, Zixi
author_sort Ou, Lihui
collection PubMed
description [Image: see text] An improved density functional theory-based H coverage-dependent electrochemical model with explicit solvent effect is proposed for Cu(111), which is used to identify potential-dependent initial competitive CO(2) electroreduction pathways considering HER. We find that a chemisorbed CO(2) molecule at the present electrode/aqueous interface can be spontaneously formed and the overpotentials can affect its coordination pattern. The Eley–Rideal mechanism may be more favorable during the initial CO(2) electroreduction into CO, whereas chemisorbed CO(2) reacting with adsorbed H into HCOO(–) via the Langmuir–Hinshelwood mechanism is more facile to occur. The analyses of energetics suggest that the low overpotentials have a negligible influence on CO and HCOO(–) formation, and HCOO(–) species with monodentate and bidentate configurations may also parallelly form with the surmountable barriers at room temperature. However, the high potentials have an interruptive effect on initial CO(2) electroreduction because of the significantly increased barriers, indicating that the chemisorbed CO(2) can be stabilized by imposing more negative potentials and thus going against initial CO(2) electroreduction. By analyzing the competing HER with initial CO(2) electroreduction into CO, we find that HER is competitive with initial CO formation because of the required lower overpotentials. Simultaneously, the present study shows that the blocked Cu surface by adsorbed H and CO can explain why the initial CO formation pathway is unfavorable at the high overpotentials. Our present conclusions can also confirm the previous experimental report on initial formation of CO and HCOO(–).
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spelling pubmed-72883612020-06-15 Potential-Dependent Competitive Electroreduction of CO(2) into CO and Formate on Cu(111) from an Improved H Coverage-Dependent Electrochemical Model with Explicit Solvent Effect Ou, Lihui He, Zixi ACS Omega [Image: see text] An improved density functional theory-based H coverage-dependent electrochemical model with explicit solvent effect is proposed for Cu(111), which is used to identify potential-dependent initial competitive CO(2) electroreduction pathways considering HER. We find that a chemisorbed CO(2) molecule at the present electrode/aqueous interface can be spontaneously formed and the overpotentials can affect its coordination pattern. The Eley–Rideal mechanism may be more favorable during the initial CO(2) electroreduction into CO, whereas chemisorbed CO(2) reacting with adsorbed H into HCOO(–) via the Langmuir–Hinshelwood mechanism is more facile to occur. The analyses of energetics suggest that the low overpotentials have a negligible influence on CO and HCOO(–) formation, and HCOO(–) species with monodentate and bidentate configurations may also parallelly form with the surmountable barriers at room temperature. However, the high potentials have an interruptive effect on initial CO(2) electroreduction because of the significantly increased barriers, indicating that the chemisorbed CO(2) can be stabilized by imposing more negative potentials and thus going against initial CO(2) electroreduction. By analyzing the competing HER with initial CO(2) electroreduction into CO, we find that HER is competitive with initial CO formation because of the required lower overpotentials. Simultaneously, the present study shows that the blocked Cu surface by adsorbed H and CO can explain why the initial CO formation pathway is unfavorable at the high overpotentials. Our present conclusions can also confirm the previous experimental report on initial formation of CO and HCOO(–). American Chemical Society 2020-05-27 /pmc/articles/PMC7288361/ /pubmed/32548457 http://dx.doi.org/10.1021/acsomega.0c00227 Text en Copyright © 2020 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Ou, Lihui
He, Zixi
Potential-Dependent Competitive Electroreduction of CO(2) into CO and Formate on Cu(111) from an Improved H Coverage-Dependent Electrochemical Model with Explicit Solvent Effect
title Potential-Dependent Competitive Electroreduction of CO(2) into CO and Formate on Cu(111) from an Improved H Coverage-Dependent Electrochemical Model with Explicit Solvent Effect
title_full Potential-Dependent Competitive Electroreduction of CO(2) into CO and Formate on Cu(111) from an Improved H Coverage-Dependent Electrochemical Model with Explicit Solvent Effect
title_fullStr Potential-Dependent Competitive Electroreduction of CO(2) into CO and Formate on Cu(111) from an Improved H Coverage-Dependent Electrochemical Model with Explicit Solvent Effect
title_full_unstemmed Potential-Dependent Competitive Electroreduction of CO(2) into CO and Formate on Cu(111) from an Improved H Coverage-Dependent Electrochemical Model with Explicit Solvent Effect
title_short Potential-Dependent Competitive Electroreduction of CO(2) into CO and Formate on Cu(111) from an Improved H Coverage-Dependent Electrochemical Model with Explicit Solvent Effect
title_sort potential-dependent competitive electroreduction of co(2) into co and formate on cu(111) from an improved h coverage-dependent electrochemical model with explicit solvent effect
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7288361/
https://www.ncbi.nlm.nih.gov/pubmed/32548457
http://dx.doi.org/10.1021/acsomega.0c00227
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